Reverse flow reactors with selective flue gas management

ABSTRACT

Systems and methods are provided for improving the operation of groups of reverse flow reactors by operating reactors in a regeneration portion of the reaction cycle to have improved flue gas management. The flue gas from reactor(s) at a later portion of the regeneration step can be selectively used for recycle back to the reactors as a diluent/heat transport fluid. The flue gas from a reactor earlier in a regeneration step can be preferentially used as the gas vented from the system to maintain the desired volume of gas within the system. This results in preferential use of higher temperature flue gas for recycle and lower temperature flue gas for venting from the system. This improved use of flue gas within a reaction system including reverse flow reactors can allow for improved reaction performance while reducing or minimizing heat losses during the regeneration portion of the reaction cycle.

CROSS REFERENCE TO RELATED APPLICATION

This application claims priority to U.S. Provisional Application Ser.No. 62/837,928 filed Apr. 24, 2019, which is herein incorporated byreference in its entirety.

FIELD

This invention relates to management of flue gas flow during operationof reverse flow reactors.

BACKGROUND

Reverse flow reactors are an example of a reactor type that isbeneficial for use in processes with cyclic reaction conditions. Forexample, due to the endothermic nature of reforming reactions,additional heat needs to be introduced on a consistent basis into thereforming reaction environment. Reverse flow reactors can provide anefficient way to introduce heat into the reaction environment. After aportion of the reaction cycle used for reforming or another endothermicreaction, a second portion of the reaction cycle can be used forcombustion or another exothermic reaction to add heat to the reactionenvironment in preparation for the next reforming step. U.S. Pat. Nos.7,815,873 and 8,754,276 provide examples of using reverse flow reactorsto perform various endothermic processes in a cyclic reactionenvironment.

U.S. Pat. No. 7,740,289 describes production of synthesis gas in areverse flow reactor by steam reforming followed by incompletecombustion of remaining hydrocarbons at elevated temperature andpressure. In addition to providing additional synthesis gas, theincomplete combustion provides heat to the reactor. In the methoddescribed in U.S. Pat. No. 7,740,289, the reversal of flow is achievedby alternating the end of the reactor used for input of the reactantflows for performing the steam reforming and incomplete combustion. Theresulting synthesis gas can then be used for production of methanol.

U.S. Patent Application Publication 2012/0111315 describes an in-situvaporizer and recuperator that is suitable for use with an alternatingflow system, such as a pressure swing reformer.

SUMMARY

In various aspects, a method for operating a plurality of reactors isprovided. The method includes reacting a first mixture comprising fueland 0.1 vol % or more of O₂ under first combustion conditions in a firstcombustion zone within a first reactor, to form a first flue gascomprising a first temperature of 350° C. or more, and to heat one ormore surfaces in a first reaction zone to a regenerated surfacetemperature of 800° C. or more. The first reaction zone can include acatalyst composition. At least a portion of the first flue gas and atleast a portion of a second flue gas can be passed into a secondreactor. The method an further include reacting a second mixturecomprising fuel, 0.1 vol % or more of O₂, the at least a portion of thefirst flue gas, and the at least a portion of the second flue gas undersecond combustion conditions in a second combustion zone within thesecond reactor to form the second flue gas, the second flue gas having atemperature of between 200° C. to the first temperature, and to heat oneor more surfaces in a second reaction zone. The second mixture caninclude a volume ratio of the at least a portion of the first flue gasto the at least a portion of the second flue gas of 1.5 or more. A firstreactant stream can be exposed to the one or more surfaces in the firstreaction zone to increase the temperature of the first reactant stream.The first reactant stream can also be exposed to the catalystcomposition in the first reaction zone at a temperature of 800° C. ormore to form a first product stream, a direction of flow for the firstreactant stream within the first reaction zone being reversed relativeto a direction of flow for the first mixture.

In various aspects, a system including a plurality of reverse flowreactors is also provided. The system can include a manifold comprisinga loop flow path, a recycle outlet, a second outlet, a first loop valve,and a second loop valve. The second outlet can be located between thefirst loop valve and the second loop valve. The system can furtherinclude a plurality of reverse flow reactors, with each reverse flowreactor including a recycle gas inlet, a recycle gas inlet valve, a fluegas outlet, and a flue gas outlet valve. The flue gas outlet valve ofeach reverse flow reactor can be in fluid communication with themanifold. The flue gas outlet of at least one reverse flow reactor canbe in fluid communication with the manifold via an open flue gas outletvalve. Additionally, the system can include a recycle compressor influid communication with the recycle outlet and each recycle gas inletvalve. The recycle gas inlet of the at least one reverse flow reactorcan be in fluid communication with the recycle compressor via an openrecycle gas inlet valve.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an example of a configuration for cascading of flue gasfrom a higher pressure reverse flow reactor to a lower pressure reverseflow reactor.

FIG. 2 shows an example of a configuration for using a plurality ofreverse flow reactors to perform hydrocarbon reforming.

FIG. 3 shows another example of a configuration for cascading of fluegas from a higher pressure reverse flow reactor to a lower pressurereverse flow reactor.

FIG. 4 shows an example of a configuration for selecting flue gas flowsfor use as recycle streams to reverse flow reactors.

FIG. 5 shows a temperature profile for gas exhausted from a reverse flowreactor during a reforming cycle.

FIG. 6 shows an example of a manifold configuration for use with aplurality of reverse flow reactors.

FIG. 7 shows conversion during a reforming cycle with variousregeneration inlet temperatures.

FIG. 8 shows hydrogen production and fuel consumption during a reformingcycle with various regeneration inlet temperatures.

FIG. 9 shows temperature profiles for a reverse flow reactor during areforming cycle with various regeneration inlet temperatures.

FIG. 10 shows a temperature profile relative to location within areactor during a reforming cycle with a regeneration flue gas exittemperature of less than 500° C.

FIG. 11 shows a temperature profile relative to location within areactor during a reforming cycle with a regeneration flue gas exittemperature of greater than 500° C.

FIG. 12 schematically shows an example of operation of a reverse flowreactor.

FIG. 13 schematically shows an example of a reverse flow reactor.

DETAILED DESCRIPTION

All numerical values within the detailed description and the claimsherein are modified by “about” or “approximately” the indicated value,and take into account experimental error and variations that would beexpected by a person having ordinary skill in the art.

Overview

In various aspects, systems and methods are provided for improving theoperation of groups of reverse flow reactors when operating in a mannerto provide a continuous or semi-continuous flow of output. In suchaspects, where a plurality of reactors are used to allow for differentreactors to be in different stages of a reaction cycle, the reactors ina regeneration portion of the reaction cycle can be operated to haveimproved flue gas management. For example, reactors toward the end ofregeneration can have a higher flue gas exhaust temperature thanreactors earlier in the regeneration step. The flue gas from reactor(s)at a later portion of the regeneration step can be selectively used forrecycle back to the reactors as a diluent/heat transport fluid. The fluegas from a reactor earlier in a regeneration step can be preferentiallyused as the gas vented from the system to maintain the desired volume ofgas within the system. This improved use of flue gas within a reactionsystem including reverse flow reactors can allow for improved reactionperformance while reducing or minimizing heat losses during theregeneration portion of the reaction cycle.

Reverse flow reactors and/or other reactors with flows in oppositedirections at different stages of a reaction cycle can be useful whenperforming endothermic reactions at elevated temperatures. Examples ofelevated temperatures correspond to 600° C. or more, or 800° C. or more,such as up to 1600° C. or possibly still higher. A flow from a firstdirection, corresponding to a combustion or regeneration flow, can beused to heat a reaction zone within the reactor to a desiredtemperature. The reagents for a desired reaction can then be passed inusing a flow in the opposite direction. The heat stored within thereaction zone of the reactor during the regeneration step is used toprovide heat for the desired endothermic reaction.

One of the challenges in operating a reverse flow reactor is managingthe introduction of heat during the regeneration step. Introducing alarger amount of heat into the reactor during the regeneration step canallow for an increased amount of the corresponding endothermic reactionduring the reaction step. However, the amount of heat that can beintroduced is constrained by the need to avoid excessive temperaturespikes in localized areas. For example, performing too much combustionat a single location could result in exceeding a maximum temperature forthe structural materials and/or internal components of the reactor.

In order to overcome this difficulty, a diluent gas can be introducedduring the regeneration step. The reactor can also be pressurized duringregeneration to increase the amount of diluent gas per unit volume. Insome aspects, the diluent gas corresponds to nitrogen or a compositionthat is substantially composed of nitrogen (i.e., air). The diluent gasabsorbs a portion of the heat generated during combustion and carriesthe heat to downstream locations within the reactor (relative to thedirection of flow in the regeneration step). Thus, the diluent can actas a heat transport fluid. This can allow additional heat to beintroduced into the reactor while reducing the maximum temperature atany location. While adding a diluent to the input flow duringregeneration can be effective for creating a broader high temperaturereaction zone, the diluent and combustion products retain at least someheat as they exit from the reactor. The diluent and combustion productsare exhausted from the reactor as a flue gas.

It has been discovered that a substantial portion of the waste heat in areverse flow reactor system is lost due to exhaust of flue gas duringregeneration of the reactor(s). However, it is difficult to fullyrecover the heat energy from the flue gas exhausted from such flue gas.As the temperature increases, the amount of waste heat can increaserapidly. For example, in a conventional reverse flow reactorconfiguration, increasing the exit temperature for the flue gas duringregeneration from 300° C. to 400° C. can result in a roughly 20%increase in the amount of waste energy that is lost from the system.

Although higher flue gas exit temperatures result in additional loss ofwaste energy, higher temperatures can also provide substantial benefitsfor the endothermic reaction performed in the reverse flow reactor.These benefits can include, but are not limited to, improved reactionkinetics for the endothermic reaction; increased product yields;increased single pass conversion of reactants; improved selectivity fordesired products; and/or other possible benefits. For example, whenperforming steam reforming, increasing the exit temperature of thereactor during regeneration can allow for a substantial increase inconversion of methane (or other hydrocarbons) to the desired syngasproduct.

Based on the above, it would be desirable to develop systems and methodsthat can allow for the improved reaction benefits of having a higherflue gas exhaust temperature while also achieving the reduced energycosts of having a lower flue gas exhaust temperature.

It has been discovered that the difficulties with loss of waste heatfrom a reaction system including reverse flow reactors can be reduced orminimized by improving the management of flue gas within a reactionsystem. This can be achieved, for example, by at least partiallysegregating flue gas from reactors at later stages of regeneration fromflue gas exhausted from reactors at earlier stages of regeneration. This(at least partial) segregation can allow flue gas at higher temperaturesto be preferentially used as the recycle gas/heat transport fluid in thereaction system. By preferentially using higher temperature flue gas forrecycle, any flue gas that is passed out of the reaction system cansubstantially correspond to lower temperature flue gas. This is incontrast to conventional configurations, where the flue gas fromreactors at various stages of regeneration may be mixed together priorto recycle or passage out of the reaction system.

The segregation of higher temperature flue gas and lower temperatureflue gas can be observed based on the ratio of flue gas from variousreactors that is used for recycle. The benefits of segregation can beobserved based on selective use of high temperature flue gas as heattransfer fluid into a single reactor, or based on selective use of hightemperature flue gas to a plurality of reactors (such as up to allreactors in a regeneration portion of the reaction cycle). When hightemperature flue gas is segregated for delivery to a plurality ofreactors, a volume ratio of high temperature flue gas to low temperatureflow gas delivered to the plurality of reactors can be 1.5 or more, or2.0 or more, or 3.0 or more, or 5.0 or more, such as up to havingsubstantially all of the flue gas correspond to high temperature fluegas. When high temperature flue gas from one reactor is segregated fordelivery to another single reactor (such as by cascade), a volume ratioof high temperature flue gas to low temperature flow gas delivered tothe plurality of reactors can be 3.0 or more, or 5.0 or more, or 8.0 ormore, such as up to having substantially all of the flue gas correspondto high temperature flue gas.

By segregating the flue gas flows, the advantages of high temperatureoperation can be realized while reducing or minimizing the amount ofwaste heat. Allowing the regeneration step to complete at an increasedtemperature flue gas exhaust temperature can provide reactivitybenefits. By selectively using the resulting high temperature flue gasfor recycle to other reactors that are earlier in the regeneration step,the flue gas passed out of the system substantially corresponds to lowertemperature flue gas, thus reducing or minimizing energy waste.

Based on segregation of higher temperature and lower temperature fluegas, energy use in the reverse flow reactors can be reduced whilemaintaining similar operation. Alternatively, the maximum exittemperature of flue gas from the reactors can be increased whilemaintaining similar energy usage. Increasing the maximum exittemperature of the flue gas can allow for higher temperature operationand/or increased flow through the reactor, resulting in benefits such asbetter kinetics for a desired reaction, increased yields, and/or otherbenefits from higher temperature operation. More generally, anyconvenient combination of the benefits of reduced energy usage and/orimproved operation of the reaction can be selected.

In this discussion, unless otherwise specified, description oftemperatures within the reaction zone corresponds to temperaturesmeasured at the location where the maximum temperature occurs in thereaction zone at the end of the regeneration step. The location of themaximum temperature in the reaction zone at the end of the regenerationstep is typically at or near the boundary between the reaction zone andthe recuperation zone. The boundary between the reaction zone and therecuperation zone is defined as the location where the catalyst for theendothermic reaction begins in the reactor.

In this discussion, unless otherwise specified, all volume ratioscorrespond to volume ratios where the quantities in the ratio arespecified based on volume at standard temperature and pressure (20° C.,100 kPa). This allows volume ratios to be specified consistently eventhough two flue gas volumes being compared may exist at differenttemperatures and pressures. When a volume ratio is specified for fluegases being delivered into a reactor, the corresponding flow rate of gasfor a unit time under standard conditions can be used for thecomparison.

Configuration Example High Pressure to Low Pressure Cascade

One option for segregating high temperature flue gas can be to use acascade configuration, so that substantially all of the flue gasgenerated at high temperature by regeneration is passed into a reactorthat is in an earlier stage of regeneration. This can be achieved, forexample, by performing later portions of regeneration at a higherpressure. The resulting higher pressure flue gas can then be passed intoa lower pressure reactor without requiring additional compression.

FIG. 2 shows an example of a reaction system including multiple reverseflow reactors. Although a total of five reactors are shown in FIG. 2(and in various other figures), it is understood that any convenientnumber of reactors can be used. By using multiple reactors, a continuousor substantially continuous stream of reaction product can be providedas input to downstream parts of a refinery, chemical plant, or otherfacility.

In FIG. 2, reactors 210 and 220 correspond to reactors in theregeneration portion of the reaction cycle. Reactors 240 and 250correspond to reactors in the endothermic reaction portion of thereaction cycle. For example, reactors 240 and 250 can perform steamreforming, where an input stream 242 of steam and methane (and/or otherreformable organics) is converted to a synthesis gas product 245.Reactor 230 corresponds to a reactor that is in-between the regenerationand reaction portions of the cycle. Depending on the length of eachportion of the cycle, reactor 230 can alternatively correspond toanother reactor in the regeneration portion of the cycle or anotherreactor in the reaction portion of the cycle. It is understood that therepresentation in FIG. 2 corresponds to a snapshot of the system at agiven point in time. As time progresses, the individual reactors willprogress from reaction to regeneration and back again to reaction.

In FIG. 2, reactors 210 and 220 are at different stages of regeneration.Reactor 210 is at an earlier stage of regeneration, while reactor 220 isat a later stage. During regeneration, the flue gas exhausted from areactor is initially at a lower temperature. As regeneration progresses,the temperature of the flue gas increases. Thus, a reactor at a laterstage of regeneration can exhaust a flue gas having a higher flue gastemperature, such as a flue gas having a temperature of 350° C. or more,or 400° C. or more, or 450° C. or more, or 500° C. or more, such as upto 700° C. or possibly higher. By contrast, a reactor at an earlierstage of regeneration can have a flue gas exhaust temperature of lessthan 500° C., or less than 450° C., or less than 400° C., or less than350° C., such as down to 170° C., or down to 200° C.

In the configuration shown in FIG. 2, reactor 210 and reactor 220 areoperated at the same pressure. Compressor 213 can be used to increasethe fuel and oxidant feed 205 to the pressure used for both reactors.

In addition to fuel and oxidant feed 205, reactors in regeneration alsoreceive flue gas as a heat transfer fluid. In the configuration shown inFIG. 2, the flue gas 215 from reactor 210 and flue gas 225 from reactor220 are mixed to form a common flue gas stream 209. The majority ofcommon flue gas stream 209 is passed through a heat recovery stage, suchas a waste heat boiler 260, followed by compression 263 to increase therecycled flue gas to the same pressure as fuel and oxidant feed 205. Theremaining portion of flue gas stream 209 is passed out of the reactionsystem, in order to maintain a desired level of gas within the reactionsystem.

It has been discovered that improvements in fuel usage and/or reactionkinetics can be achieved by modifying how flue gas is recycled to thereactors in regeneration. One example of an improved configuration canbe to cascade flue gas from reactor(s) at a later stage of regenerationto reactor(s) at an earlier stage of regeneration. By cascading thehigher temperature flue gas to another reactor in regeneration, thehigher temperature flue gas can preferentially be used to further heat areactor in regeneration. In order to perform the cascade, the reactorincluding the higher temperature flue gas can be regenerated at a higherpressure. For example, the pressure of the reactor in the highertemperature portion of the regeneration cycle can be greater than thepressure of the reactor in the lower temperature portion of theregeneration cycle by 100 kPa or more, or 150 kPa or more, or 200 kPa ormore. Any convenient pressure differential would be fine, such as up to1500 kPa or possibly still more, but still higher pressure differentialsmay have lower overall efficiency due to the pressure drop. The flue gaspassed out of the reaction system can be drawn from the remaining lowertemperature flue gas, thus reducing or minimizing the amount of heatlost or wasted.

FIG. 1 shows an example of a configuration where flue gas is cascadedfrom a reactor 120 at a later stage of regeneration to a reactor 110 atan earlier stage of regeneration. In the configuration shown in FIG. 1,reactor 110 is operated at a different pressure than reactor 120. Forexample, reactor 110 can be operated at a first pressure (such as 10 baror ˜1000 kPa-g) while reactor 120 can be operated at a second, higherpressure (such as 12 bar or ˜1200 kPa-g). The pressure differentialbetween reactors 110 and 120 can be maintained in part based on asupplemental compressor. For example, primary compressor 113 can be usedto increase the fuel and oxidant feed 105 to the first pressure used forreactors in early stages of regeneration. Supplemental compressor 123can be used to further increase the fuel and oxidant feed 105 to thesecond pressure for reactors in later stages of regeneration. In variousaspects, the pressure differential between cascaded reactors can be 100kPa or more, or 150 kPa or more, or 200 kPa or more. Similar to FIG. 2,reactor 130 is in an idle phase. Reactors 140 and 150 are in thereaction step for conversion of hydrocarbon-containing feed 142 intosynthesis gas 145.

Instead of forming a common flue gas stream, in the configuration inFIG. 1, flue gas 125 from reactor 120 is cascaded into reactor 110. Insome aspects, the pressure differential between reactor 120 and reactor110 can be sufficiently great so that no additional compression isneeded to pass flue gas 125 into reactor 110. Flue gas 115 from reactor110 can be divided into at least two portions. A first portion 111 canbe compressed 163 prior to recycling into reactor 120. A remainingportion 109 can be passed out of the reaction system.

It is noted that the cascade of flue gas from reactor 120 to reactor 110in FIG. 1 corresponds to direct fluid communication between reactor 120and reactor 110. This is defined as fluid communication between twoprocess elements without an intervening process element thatsubstantially alters the pressure, temperature, or composition of thefluid. In this discussion, substantial alteration of the pressurecorresponds to a change in pressure of 20 kPa or more, while substantialalteration of temperature corresponds to a temperature change of 10° C.or more.

FIG. 3 shows another configuration for cascading of flue gas from ahigher pressure reactor to a lower pressure reactor. In FIG. 3, the fluegas 325 from reactor 320 is cascaded to both reactor 370 and reactor371. Reactor 370 can be at an early portion of the regeneration step,such as having a flue gas exit temperature of less than 300° C., whilereactor 371 can have a flue gas exit temperature between 300° C. and400° C. In some aspects, the gas flow in a later stage of regenerationcan be greater than the gas flow in an earlier stage of regeneration.Having different gas flows at different portions of regeneration canimprove thermal efficiency while also providing flexibility for designof a reaction system.

In the example shown in FIG. 3, the flow into reactor 320 is roughlytwice the flow into reactors 370 and 371. This can allow flue gas 325 tobe split for cascading into both reactor 370 and reactor 371. In theconfiguration shown in FIG. 3, flue gas 375 and flue gas 376 are shownas being passed into a common conduit for either recycle or exit fromthe system. Optionally, flue gas 376 can be preferentially used forrecycle to reactor 320 (after compression) while any flue gas that exitsthe system can preferentially be drawn from flue gas 375.

Configuration Example Selector Valves

Another option for segregating high temperature flue gas can be to use aconfiguration with selector valves. The selector valves can be used todivert flue gas from a regenerating reactor for a desired use, so thatsubstantially all of the flue gas generated at high temperature byregeneration is passed into a reactor that is in an earlier stage ofregeneration.

FIG. 4 shows an example of a configuration using valves to control theflow of flue gas from a plurality of reactors in a regeneration step. InFIG. 4, reactor 410 and reactor 420 can (optionally) be operated at thesame or similar pressures. This can allow compressor 413 to be used toincrease the fuel and oxidant feed 405 to the pressure used for bothreactors.

In FIG. 4, selector valve 418 controls the direction of flow for fluegas 415. Similarly, selector valve 428 controls the direction of flowfor flue gas 425. Depending on the flue gas with a higher temperature,selector valve 418 and selector valve 428 can be used to recycle fluegas back to the reactors as a heat transport fluid or to pass portionsof the flue gas out of the system. It is noted that the amount of fluegas passed out of the reaction system may be smaller than the flue gasflow from a reactor. Thus, in some aspects, the selector valve for alower temperature reactor can divert a portion of the flue gas forrecycle while diverting another portion of exit from the reactionsystem.

Depending on the aspect, the valve position for the selector valves(recycle, exit from the system) can be set in any convenient manner. Oneoption can be to set the valve position based on time. The length of areaction plus regeneration cycle can stay relatively constant duringoperation, so the time periods when a flue gas corresponds to a “hot”flue gas versus a “cold” flue gas are therefore known in advance.Another option could be to detect the temperature of flue gas streamsand switch the valve positions based on the relative temperatures.

FIG. 5 shows an example of the exit temperature profile for gasesexhausted from a reverse flow reactor that was used for steam reforming.In the example shown in FIG. 5, the temperature for gases exhausted fromthe reactor during both the reaction step and the regeneration step areshown. The regeneration step corresponds to the portions of FIG. 5 wherethe flue gas temperature is increasing.

As shown in FIG. 5, the flue gas exit temperature during regenerationvaried from a low temperature around 200° C. to a high temperaturearound 700° C. One option for managing flue gas having the temperatureprofile in FIG. 5 would be to use the flue gas generated between 60seconds and 75 seconds as “low temperature” flue gas, and the flue gasgenerated between 75 seconds and 90 seconds as “high temperature” fluegas. This would correspond to using flue gas with temperatures between200° C. and 500° C. as “low temperature” flue gas, and flue gas withtemperatures between 500° C. and 700° C. as “high temperature” flue gas.

Configuration Example Ring Manifold with Valves

Still another option for segregating high temperature flue gas from lowtemperature flue gas can be based on use of a manifold and valves toallow for control of the direction of gas flow in the manifold. In thistype of option, a valve associated with each reactor and/or the manifoldconnection to each reactor can allow or prevent fluid communicationbetween a reactor and the manifold. This type of valve can be closed,for example, while a reactor is in the reaction step and then openedwhen the regeneration step starts. The manifold can also have exitlocations for gas that is to be passed to the recycle compressor forrecycle to the reactors, and for gas that is to be passed through anexpander to recover energy from the gas prior to leaving the reactionsystem.

In addition to the valves to control fluid communication between eachreactor and the manifold, additional valves can be used to control thedirection of fluid (gas) flow within the manifold. For example, themanifold can be organized in a ring or other closed loop/continuousconfiguration, so that when all manifold valves are open, fluidcommunication is available between all points in the manifold in eitherdirection of flow. At least two valves can then be used to control fluidflow within the manifold. By selectively opening and closing the atleast two valves, the distance of the available fluid flow path for eachreactor to the two exit locations can be controlled. By controlling thedistance of the fluid flow path, the reaction system can be operated sothat the high temperature flue gas is closer to the recycle compressorexit than the expander exit. Similarly, control of the valves can alsocause the low temperature flue gas to be closer to the expander exitthan the recycle compressor exit.

FIG. 6 shows an example of how a ring manifold configuration can beoperated to selectively use high temperature flue gas for recycle to thereactors. In FIG. 6, five different snapshots in time are shown. In eachsnapshot, one reactor corresponds to a reactor 620 which is exhaustinghigh temperature flue gas during the regeneration step. In other words,reactor 620 is in the later portion of the regeneration step. Anotherreactor corresponds to a reactor 610 which is exhausting low temperatureflue gas. The remaining reactors correspond to reactors that are eitheridle 631 or in the reaction step 630, and therefore not currently influid communication with the manifold. The identity of reactor 620 andreactor 610 changes in each snapshot due to the cyclic nature of theoverall reaction, where the reactors switch from reaction toregeneration within each cycle. Because the identity of the reactorschanges in each snapshot, each reactor is labeled in each snapshot. Theremaining elements are only labeled in FIG. 6A.

FIG. 6A shows one of the snapshots of the manifold. In FIG. 6A, valve670 is open, while valve 681 is closed. Because valve 670 is open,reactor 610 is closer to the expander outlet 654 than reactor 620. Bycontrast, because valve 681 is closed, the flow path from reactor 620 torecycle compressor outlet 656 is shorter than the flow path for reactor610. Although some mixing of the flue gases from reactor 610 and reactor620 may occur, the substantial portion of the gas that exits throughexpander outlet 654 will come from reactor 610, while the substantialportion of the gas that exits through recycle compressor outlet 656 willcome from reactor 620. If desired, tracer gases could be used incombination with a detector (such as infrared spectroscopy or massspectrometry) to determine the relative proportions of gas from reactor610 and reactor 620 that leave the manifold through expander exit 654and recycle compressor exit 656 under various pressure and flow rateconditions.

As the reaction cycle progresses, the identity of reactor 620 andreactor 610 will change, as one reactor finishes the regeneration cycleand another reactor enters the regeneration cycle. FIG. 6B shows theconfiguration after the shift in the identity of reactor 620 and reactor610. Valve 670 remains open while valve 681 remains closed. As shown inFIG. 6B, the new location for reactor 620 still has a shorter fluid flowpath to the recycle compressor outlet 656 than the new location forreactor 610, while reactor 610 has a shorter fluid flow path to expanderoutlet 654.

As the reaction cycle progresses further, the configuration can passthrough states that correspond to FIG. 6C, FIG. 6D, and FIG. 6E. Asshown in FIG. 6C and FIG. 6D, keeping valve 670 open and valve 681closed maintains the desired manifold configuration of having theshortest fluid flow path between reactor 620 and the recycle compressoroutlet 656 and the shortest fluid flow path between reactor 610 andexpander outlet 654.

In FIG. 6E, the states of the valves are changed. In FIG. 6E, valve 671is now closed, while valve 680 is open. It is noted that reactor 620 andreactor 610 are on opposite sides of closed valve 671 in FIG. 6E. Thisshift in the opened and closed valves allows the manifold configurationto remain in the desired condition, where the fluid flow path fromreactor 620 to the recycle compressor outlet 656 is the shortest flowpath, and the fluid flow path from reactor 610 to the expander exit isthe shortest flow path.

Example of Reverse Flow Reactor Configuration

For endothermic reactions operated at elevated temperatures, such ashydrocarbon reforming, a reverse flow reactor can provide a suitablereaction environment for providing the heat for the endothermicreaction.

In a reverse flow reactor, the heat needed for an endothermic reactionmay be provided by creating a high-temperature heat bubble in the middleof the reactor. A two-step process can then be used wherein heat is (a)added to the reactor bed(s) or monolith(s) via in-situ combustion, andthen (b) removed from the bed in-situ via an endothermic process, suchas reforming, pyrolysis, or steam cracking. This type of configurationcan provide the ability to consistently manage and confine the hightemperature bubble in a reactor region(s) that can tolerate suchconditions long term. A reverse flow reactor system can allow theprimary endothermic and regeneration processes to be performed in asubstantially continuous manner.

As an example, a reverse flow reactor system can include first andsecond reactors, oriented in a series relationship with each other withrespect to a common flow path, and optionally but preferably along acommon axis. The common axis may be horizontal, vertical, or otherwise.In other examples, a reverse flow reactor system can correspond to asingle reactor that includes both a reaction zone and a recuperationzone.

During a regeneration step, reactants (e.g., fuel and oxygen) arepermitted to combine or mix in a reaction zone to combust therein,in-situ, and create a high temperature zone or heat bubble inside amiddle portion of the reactor system. The heat bubble can correspond toa temperature that is at least about the initial temperature for theendothermic reaction. Typically, the temperature of the heat bubble canbe greater than the initial temperature for the endothermic reaction, asthe temperature will decrease as heat is transferred from the heatbubble in a middle portion of the reactor toward the ends of thereactor. In some aspects, the combining can be enhanced by a reactantmixer that mixes the reactants to facilitate substantially completecombustion/reaction at the desired location, with the mixer optionallylocated between the first and second reactors. The combustion processcan take place over a long enough duration that the flow of first andsecond reactants through the first reactor also serves to displace asubstantial portion, (as desired) of the heat produced by the reaction(e.g., the heat bubble), into and at least partially through the secondreactor, but preferably not all of the way through the second reactor toreduce or minimize waste of heat and overheating the second reactor.This heat is transferred, for example, to one or more surfaces in thesecond reactor and/or in the reaction zone for the endothermic reactionin a reactor. The flue gas may be exhausted through the second reactor,but preferably most of the heat is retained within the second reactor.The amount of heat displaced into the second reactor during theregeneration step can also be limited or determined by the desiredexposure time or space velocity that the hydrocarbon feed gas will havein the endothermic reaction environment. In aspects where a singlereactor is used, the heat produced by the reaction can be displaced intoand/or at least partially through the reaction zone of the reactor, butpreferably the displacement can also reduce or minimize waste of heatdue to exit of heated gas from the reactor.

After regeneration or heating the second reactor media (which caninclude and/or correspond to one or more surfaces including a catalystfor an endothermic reaction), in the next/reverse step or cycle,reactants for the endothermic reaction methane (and/or natural gasand/or another hydrocarbon) can be supplied or flowed through the secondreactor, from the direction opposite the direction of flow during theheating step. For example, in a reforming process, methane (and/ornatural gas and/or another hydrocarbon) can be supplied or flowedthrough the second reactor. The methane can contact the hot secondreactor and mixer media, in the heat bubble region, to transfer the heatto the methane for reaction energy.

For some aspects, the basic two-step asymmetric cycle of a reverse flowregenerative bed reactor system is depicted in FIGS. 12A and 12B of FIG.12 in terms of a reactor system having two zones/reactors; a first orrecuperator/quenching zone (7) and a second or reaction zone (1). Boththe reaction zone (1) and the recuperator zone (7) can containregenerative monoliths and/or other regenerative structures formed froma doped ceramic composition. Regenerative monoliths or otherregenerative structures, as used herein, comprise materials that areeffective in storing and transferring heat as well as being effectivefor carrying out a chemical reaction. The regenerative monoliths and/orother structures can correspond to any convenient type of material thatis suitable for storing heat, transferring heat, and catalyzing areaction. Examples of structures can include bedding or packing materialceramic beads or spheres, ceramic honeycomb materials, ceramic tubes,extruded monoliths, and the like, provided they are competent tomaintain integrity, functionality, and withstand long term exposure totemperatures in excess of 1200° C., or in excess of 1400° C., or inexcess of 1600° C., which can allow for some operating margin. In someaspects, the catalytic ceramic monolith and/or other catalytic ceramicstructure can be used without the presence of an additional washcoat.

To facilitate description of FIG. 12, the reactor is described hereinwith reference to a reforming reaction. It is understood that otherconvenient types of endothermic reactions can generally be performedusing a reverse flow reactor, such as the reactor shown in FIG. 12.

As shown in FIG. 12B of FIG. 12, at the beginning of the “reaction” stepof the cycle, a secondary end 5 of the reaction zone 1 (a.k.a. herein asthe second reactor) can be at an elevated temperature as compared to theprimary end 3 of the reaction zone 1, and at least a portion (includingthe first end 9) of the recuperator or quench zone 7 (a.k.a. herein asthe first reactor), can be at a lower temperature than the reaction zone1 to provide a quenching effect for the resulting product. In an aspectwhere the reactors are used to perform reverse flow reforming, amethane-containing reactant feed (or other hydrocarbon-containingreactant feed) can be introduced via a conduit(s) 15, into a primary end3 of the reforming or reaction zone 1. In various aspects, thehydrocarbon-containing reactant feed can also contain H₂O, CO₂, or acombination thereof

The feed stream from inlet(s) 15 can absorb heat from reaction zone 1and endothermically react to produce the desired synthesis gas product.As this step proceeds, a shift in the temperature profile 2, asindicated by the arrow, can be created based on the heat transferproperties of the system. When the ceramic catalyst monolith/othercatalyst structure is designed with adequate heat transfer capability,this profile can have a relatively sharp temperature gradient, whichgradient can move across the reaction zone 1 as the reforming stepproceeds. In some aspects, a sharper temperature gradient profile canprovide for improved control over reaction conditions. In aspects whereanother type of endothermic reaction is performed, a similar shift intemperature profile can occur, so that a temperature gradient movesacross reaction zone 1 as the reaction step proceeds.

The effluent from the reforming reaction, which can include unreactedfeed components (hydrocarbons, H₂O, CO₂) as well as synthesis gascomponents, can exit the reaction zone 1 through a secondary end 5 at anelevated temperature and pass through the recuperator reactor 7,entering through a second end 11, and exiting at a first end 9. Therecuperator 7 can initially be at a lower temperature than the reactionzone 1. As the products (and optionally unreacted feed) from thereforming reaction pass through the recuperator zone 7, the gas can bequenched or cooled to a temperature approaching the temperature of therecuperator zone substantially at the first end 9, which in someembodiments can be approximately the same temperature as theregeneration feed introduced via conduit 19 into the recuperator 7during the second step of the cycle. As the reforming effluent is cooledin the recuperator zone 7, a temperature gradient 4 can be created inthe zone's regenerative bed(s) and can move across the recuperator zone7 during this step. The quenching can heat the recuperator 7, which canbe cooled again in the second step to later provide another quenchingservice and to prevent the size and location of the heat bubble fromgrowing progressively through the quench reactor 7. After quenching, thereaction gas can exit the recuperator at 9 via conduit 17 and can beprocessed for separation and recovery of the various components.

The second step of the cycle, referred to as the regeneration step, canthen begin with reintroduction of the first and second regenerationreactants via conduit(s) 19. The first and second reactants can passseparately through hot recuperator 7 toward the second end 11 of therecuperator 7, where they can be combined for exothermic reaction orcombustion in or near a central region 13 of the reactor system.

An example of the regeneration step is illustrated in FIG. 12B of FIG.12. Regeneration can entail transferring recovered sensible heat fromthe recuperator zone 7 to the reaction zone 1 to thermally regeneratethe reaction beds 1 for the subsequent reaction cycle. Regenerationgas/reactants can enter recuperator zone 7, such as via conduit(s) 19,and flow through the recuperator zone 7 and into the reaction zone 1. Indoing so, the temperature gradients 6 and 8 may move across the beds asillustrated by the arrows on the exemplary graphs in FIG. 12B, similarto but in opposite directions to the graphs of the temperature gradientsdeveloped during the reaction cycle in FIG. 12A of FIG. 12. Fuel andoxidant reactants may combust at a region proximate to the interface 13of the recuperator zone 7 and the reaction zone 1. The heat recoveredfrom the recuperator zone together with the heat of combustion can betransferred to the reaction zone, thermally regenerating theregenerative reaction monoliths and/or beds 1 disposed therein.

In some aspects, several of the conduits within a channel may convey amixture of first and second reactants, due at least in part to somemixing at the first end (17) of the first reactor. However, the numbersof conduits conveying combustible mixtures of first and second reactantscan be sufficiently low such that the majority of the stoichiometricallyreactable reactants will not react until after exiting the second end ofthe first reactor. The axial location of initiation of combustion orexothermic reaction within those conduits conveying a mixture ofreactants can be controlled by a combination of temperature, time, andfluid dynamics. Fuel and oxygen usually require a temperature-dependentand mixture-dependent autoignition time to combust. Still though, somereaction may occur within an axial portion of the conduits conveying amixture of reactants. However, this reaction can be acceptable becausethe number of channels having such reaction can be sufficiently smallthat there is only an acceptable or inconsequential level of effect uponthe overall heat balance within the reactor. The design details of aparticular reactor system can be selected so as to avoid mixing ofreactants within the conduits as much as reasonably possible.

FIG. 13 illustrates another exemplary reactor system that may besuitable in some applications for controlling and deferring thecombustion of fuel and oxidant to achieve efficient regeneration heat.FIG. 13 depicts a single reactor system, operating in the regenerationcycle. The reactor system may be considered as comprising two reactorszones. The recuperator 27 can be the zone primarily where quenchingtakes place and provides substantially isolated flow paths or channelsfor transferring both of the quenching reaction gases through thereactor media, without incurring combustion until the gasses arriveproximate or within the reactor core 13 in FIG. 12. The reformer 2 canbe the reactor where regeneration heating and methane (and/orhydrocarbon) reformation primarily occurs, and may be considered as thesecond reactor for purposes herein. Although the first and secondreactors in the reactor system are identified as separatelydistinguishable reactors, it is understood that the first and secondreactors may be manufactured, provided, or otherwise combined into acommon single reactor bed, whereby the reactor system might be describedas comprising merely a single reactor that integrates both cycles withinthe reactor. The terms “first reactor” and “second reactor” can merelyrefer to the respective zones within the reactor system whereby each ofthe regeneration, reformation, quenching, etc., steps take place and donot require that separate components be utilized for the two reactors.However, various aspects can comprise a reactor system whereby therecuperator reactor includes conduits and channels as described herein,and the reformer reactor may similarly possess conduits. Additionally oralternately, some aspects may include a reformer reactor bed that isarranged different from and may even include different materials from,the recuperator reactor bed.

As discussed previously, the first reactor or recuperator 27 can includevarious gas conduits 28 for separately channeling two or more gasesfollowing entry into a first end 29 of the recuperator 27 and throughthe regenerative bed(s) disposed therein. A first gas 30 can enter afirst end of a plurality of flow conduits 28. In addition to providing aflow channel, the conduits 28 can also comprise effective flow barriers(e.g., which effectively function such as conduit walls) to preventcross flow or mixing between the first and second reactants and maintaina majority of the reactants effectively separated from each other untilmixing is permitted. As discussed previously, each of the first andsecond channels can comprise multiple channels or flow paths. The firstreactor may also comprise multiple substantially parallel flow segments,each comprising segregated first and second channels.

In some aspects, the recuperator can be comprised of one or moreextruded honeycomb monoliths, as described above. Each monolith mayprovide flow channel(s) (e.g., flow paths) for one of the first orsecond reactants. Each channel preferably includes a plurality ofconduits. Alternatively, a monolith may comprise one or more channelsfor each reactant with one or more channels or groups of conduitsdedicated to flowing one or more streams of a reactant, while theremaining portion of conduits flow one or more streams of the otherreactant. It is recognized that at the interface between channels, anumber of conduits may convey a mixture of first and second reactant,but this number of conduits is proportionately small.

In aspects where a monolith is used, the monolith can have anyconvenient shape suitable for use as a catalytic surface. An example ofa monolith can be an extruded honeycomb monolith. Honeycomb monolithscan be extruded structures that comprise many (e.g., a plurality,meaning more than one) small gas flow passages or conduits, arranged inparallel fashion with thin walls in between. A small reactor may includea single monolith, while a larger reactor can include a number ofmonoliths, while a still larger reactor may be substantially filled withan arrangement of many honeycomb monoliths. Each monolith may be formedby extruding monolith blocks with shaped (e.g., square or hexagonal)cross-section and two- or three-dimensionally stacking such blocksabove, behind, and beside each other. Monoliths can be attractive asreactor internal structures because they provide high heat transfercapacity with minimum pressure drop.

In some aspects, honeycomb monoliths can be characterized as having openfrontal area (or geometric void volume) between 25% and 55%, and havingconduit density between 50 and 2000 pores or cells per square inch(CPSI), or between 100 and 900 cells per square inch, or between 100cells per square inch to 600 cells per square inch. For example, in oneembodiment, the conduits may have a diameter/characteristic cell sidelength of only a few millimeters, such as on the order of roughly onemillimeter. Reactor media components, such as the monoliths oralternative bed media, can provide for channels that include a packingwith an average wetted surface area per unit volume that ranges from 50ft⁻¹ to 3000 ft⁻¹ (˜0.16 km⁻¹ to ˜10 km⁻¹), or from 100 ft⁻¹ to 2500ft⁻¹ (˜0.32 km⁻¹ to ˜8.2 km⁻¹), or from 200 ft⁻¹ to 2000 ft⁻¹ (˜0.65km⁻¹ to ˜6.5 km⁻¹), based upon the volume of the first reactor that isused to convey a reactant. These relatively high surface area per unitvolume values can aid in achieving a relatively quick change in thetemperature through the reactor, such as generally illustrated by therelatively steep slopes in the exemplary temperature gradient profilegraphs shown in FIG. 12A or 12B of FIG. 12.

Reactor media components can also provide for channels that include apacking that includes a high volumetric heat transfer coefficient (e.g.,0.02 cal/cm³s° C. or more, or 0.05 cal/cm³s° C. or more, or 0.10cal/cal/cm³s° C. or more); that have low resistance to flow (lowpressure drop); that have an operating temperature range consistent withthe highest temperatures encountered during regeneration; that have highresistance to thermal shock; and/or that have high bulk heat capacity(e.g., 0.10 cal/cm³s° C. or more, or 0.20 cal/cm³s° C. or more). As withthe high surface area values, these relatively high volumetric heattransfer coefficient values and/or other properties can aid in achievinga relatively quick change in the temperature through the reactor, suchas generally illustrated by the relatively steep slopes in the exemplarytemperature gradient profile graphs, such as in FIGS. 12A and 12B ofFIG. 12. The cited values are averages based upon the volume of reactorused for conveyance of a reactant.

In various aspects, adequate heat transfer rate can be characterized bya heat transfer parameter, ΔTHT, below 500° C., or below 100° C., orbelow 50° C. The parameter ΔTHT, as used herein, is the ratio of thebed-average volumetric heat transfer rate that is needed forrecuperation, to the volumetric heat transfer coefficient of the bed,hv. The volumetric heat transfer rate (e.g. cal/cm³ sec) that issufficient for recuperation can be calculated as the product of the gasflow rate (e.g. g/sec) with the gas heat capacity (e.g. cal/g° C.) anddesired end-to-end temperature change (excluding any reaction, e.g. °C.), and then this quantity can be divided by the volume (e.g. cm³) ofthe reactor (or portion of a reactor) traversed by the gas. Thevolumetric heat transfer coefficient of the bed, hv, can typically becalculated as the product of an area-based coefficient (e.g. cal/cm²s°C.) and a specific surface area for heat transfer (av, e.g. cm²/cm³),often referred to as the wetted area of the packing.

In some aspects, a washcoat can be added to the formed, sintered ceramiccomposition prior to exposing the composition to a reducing environmentto form dopant metal particles. A washcoat can allow the sinteredceramic composition to be impregnated with additional catalytic metal.Such additional catalytic metal can be the same as the dopant metal ordifferent.

One option for incorporating an additional catalytic metal into awashcoat can be to impregnate a catalyst support with the additionalcatalytic metal, such as by impregnation via incipient wetness. Theimpregnation can be performed with an aqueous solution of suitable metalsalt or other catalytic metal precursor, such as tetramineplatinumnitrate or rhodium nitrate hydrate. The impregnated support can then bedried and/or calcined for decomposition of the catalytic metalprecursor. A variety of temperature profiles can potentially be used forthe heating steps. One or more initial drying steps can be used fordrying the support, such as heating at a temperature from 100° C. to200° C. for 0.5 hours to 24 hours. A calcination to decompose thecatalytic metal precursor compound can be at a temperature of 200° C. to800° C. for 0.5 hours to 24 hours, depending on the nature of theimpregnated catalytic metal compound. Depending on the precursor for thecatalytic metal, the drying step(s) and/or the decomposing calcinationstep(s) can be optional. Examples of additional catalytic metals caninclude, but are not limited to, Ni, Co, Fe, Pd, Rh, Ru, Pt, Ir, Cu, Ag,Au, Zr, Cr, Ti, V, and combinations thereof.

Alternative embodiments may use reactor media other than monoliths, suchas whereby the channel conduits/flow paths may include a more tortuouspathways (e.g. convoluted, complex, winding and/or twisted but notlinear or tubular), including but not limited to labyrinthine,variegated flow paths, conduits, tubes, slots, and/or a pore structurehaving channels through a portion(s) of the reactor and may includebarrier portion, such as along an outer surface of a segment or withinsub-segments, having substantially no effective permeability to gases,and/or other means suitable for preventing cross flow between thereactant gases and maintaining the first and second reactant gasessubstantially separated from each other while axially transiting therecuperator 27. Such other types of reactor media can be suitable, solong as at least a portion of such media can be formed by sintering aceramic catalytic composition as described herein, followed by exposingsuch media to reducing conditions to activate the catalyst. For suchembodiments, the complex flow path may create a lengthened effectiveflow path, increased surface area, and improved heat transfer. Suchdesign may be preferred for reactor embodiments having a relativelyshort axial length through the reactor. Axially longer reactor lengthsmay experience increased pressure drops through the reactor. However forsuch embodiments, the porous and/or permeable media may include, forexample, at least one of a packed bed, an arrangement of tiles, apermeable solid media, a substantially honeycomb-type structure, afibrous arrangement, and a mesh-type lattice structure.

In some aspects, the reverse flow reactor can include some type ofequipment or method to direct a flow stream of one of the reactants intoa selected portion of the conduits. In the exemplary embodiment of FIG.13, a gas distributor 31 can direct a second gas stream 32 to second gasstream channels that are substantially isolated from or not in fluidcommunication with the first gas channels, here illustrated as channels33. The result can be that at least a portion of gas stream 33 is keptseparate from gas stream 30 during axial transit of the recuperator 27.In some aspects, the regenerative bed(s) and/or monolith(s) of therecuperator zone can comprise channels having a gas or fluid barrierthat isolates the first reactant channels from the second reactantchannels. Thereby, both of the at least two reactant gases that transitthe channel means may fully transit the regenerative bed(s), to quenchthe regenerative bed, absorb heat into the reactant gases, beforecombining to react with each other in the combustion zone.

In various aspects, gases (including fluids) 30 and 32 can each comprisea component that reacts with a component in the other reactant 30 and32, to produce an exothermic reaction when combined. For example, eachof the first and second reactant may comprise one of a fuel gas and anoxidant gas that combust or burn when combined with the other of thefuel and oxidant. By keeping the reactants substantially separated, thelocation of the heat release that occurs due to exothermic reaction canbe controlled. In some aspects “substantially separated” can be definedto mean that at least 50 percent, or at least 75 percent, or at least 90percent of the reactant having the smallest or limitingstoichiometrically reactable amount of reactant, as between the firstand second reactant streams, has not become consumed by reaction by thepoint at which these gases have completed their axial transit of therecuperator 27. In this manner, the majority of the first reactant 30can be kept isolated from the majority of the second reactant 32, andthe majority of the heat release from the reaction of combiningreactants 30 and 32 can take place after the reactants begin exiting therecuperator 27. The reactants can be gases, but optionally somereactants may comprise a liquid, mixture, or vapor phase.

The percent reaction for these regeneration streams is meant the percentof reaction that is possible based on the stoichiometry of the overallfeed. For example, if gas 30 comprised 100 volumes of air (80 volumes N₂and 20 Volumes O₂), and gas 32 comprised 10 volumes of hydrogen, thenthe maximum stoichiometric reaction would be the combustion of 10volumes of hydrogen (H₂) with 5 volumes of oxygen (O₂) to make 10volumes of H₂O. In this case, if 10 volumes of hydrogen were actuallycombusted in the recuperator zone (27), this would represent 100%reaction of the regeneration stream. This is despite the presence ofresidual un-reacted oxygen, because in this example the un-reactedoxygen was present in amounts above the stoichiometric requirement.Thus, in this example the hydrogen is the stoichiometrically limitingcomponent. Using this definition, less than 50% reaction, or less than25% reaction, or less than 10% reaction of the regeneration streams canoccur during the axial transit of the recuperator (27).

In various aspects, channels 28 and 33 can comprise ceramic (includingzirconia), alumina, or other refractory material capable of withstandingtemperatures exceeding 1200° C., or 1400° C., or 1600° C. Additionallyor alternately, channels 28 and 33 can have a wetted area between 50ft⁻¹ and 3000 ft⁻¹, or between 100 ft⁻¹ and 2500 ft⁻¹, or between 200ft⁻¹ and 2000 ft⁻¹.

Referring again briefly to FIG. 12, the reactor system can include afirst reactor 7 containing a first end 9 and a second end 11, and asecond reactor 1 containing a primary end 3 and a secondary end 5. Theembodiments illustrated in FIGS. 1 and 2 are merely simple illustrationsprovided for explanatory purposes only and are not intended to representa comprehensive embodiment. Reference made to an “end” of a reactormerely refers to a distal portion of the reactor with respect to anaxial mid-point of the reactor. Thus, to say that a gas enters or exitsan “end” of the reactor, such as end 9, means merely that the gas mayenter or exit substantially at any of the various points along an axisbetween the respective end face of the reactor and a mid-point of thereactor, but more preferably closer to the end face than to themid-point. Thereby, one or both of the first and second reactant gasescould enter at the respective end face, while the other is supplied tothat respective end of the reactor through slots or ports in thecircumferential or perimeter outer surface on the respective end of thereactor.

Process Example Reverse Flow Reforming and Regeneration

An example of a reaction that can be performed in a reverse flow reactorsystem is reforming of hydrocarbons under steam reforming conditions inthe presence of H₂O, under dry reforming conditions in the presence ofCO₂, or under conditions where both H₂O and CO₂ are present in thereaction environment. As a general overview of operation duringreforming in a swing reactor, such as a reverse flow reactor, aregeneration step or portion of a reaction cycle can be used to provideheat for the reactor. Reforming can then occur within the reactor duringa reforming step or portion of the cycle, with the reforming reactionconsuming heat provided during the reactor regeneration step. Duringreactor regeneration, fuel, oxidant, and a diluent are introduced intothe reactor from a regeneration end of the reactor. The bed and/ormonoliths in the regeneration portion of the reactor can absorb heat,but typically do not include a catalyst for reforming. As the fuel andoxidant pass through the regeneration section, heat is transferred fromthe regeneration section to the fuel and oxidant. Combustion does notoccur immediately, but instead the location of combustion is controlledto occur in a middle portion of the reactor. The flow of the reactantscontinues during the regeneration step, leading to additional transferof the heat generated from combustion into the reforming end of thereactor.

After a sufficient period of time, the combustion reaction is stopped.Any remaining combustion products and/or reactants can optionally bepurged. The reforming step or portion of the reaction cycle can thenstart. The reactants for reforming can be introduced into the reformingend of the reactor, and thus flow in effectively the opposite directionrelative to the flow during regeneration. The bed and/or monoliths inthe reforming portion of the reactor can include a catalyst forreforming. In various aspects, at least a portion of the catalyst cancorrespond to a catalyst formed from a ceramic composition as describedherein. As reforming occurs, the heat introduced into the reforming zoneduring combustion can be consumed by the endothermic reforming reaction.After exiting the reforming zone, the reforming products (and unreactedreactants) are no longer exposed to a reforming catalyst. As thereforming products pass through the regeneration zone, heat can betransferred from the products to the regeneration zone. After asufficient period of time, the reforming process can be stopped,remaining reforming products can optionally be collected or purged fromthe reactor, and the cycle can start again with a regeneration step.

The reforming reaction performed within the reactor can correspondreforming of methane and/or other hydrocarbons using steam reforming, inthe presence of H₂O; using dry reforming, in the presence of CO₂, orusing “bi” reforming in the presence of both H₂O and CO₂. Examples ofstoichiometry for steam, dry, and “bi” reforming of methane are shown inequations (1)-(3).

Dry Reforming: CH₄+CO₂=2CO+2H₂  (1)

Steam Reforming: CH₄+H₂O=CO+3H₂  (2)

Bi Reforming: 3CH₄+2H₂O+CO₂=4CO+8H₂.  (3)

As shown in equations (1)-(3), dry reforming can produce lower ratios ofH₂ to CO than steam reforming. Reforming reactions performed with onlysteam can generally produce a ratio of H₂ to CO of around 3, such as 2.5to 3.5. By contrast, reforming reactions performed in the presence ofCO₂ can generate much lower ratios, possibly approaching a ratio of H₂to CO of roughly 1.0 or even lower. By using a combination of CO₂ andH₂O during reforming, the reforming reaction can potentially becontrolled to generate a wide variety of H₂ to CO ratios in a resultingsyngas.

It is noted that the ratio of H₂ to CO in a synthesis gas can also bedependent on the water gas shift equilibrium. Although the abovestoichiometry shows ratios of roughly 1 or roughly 3 for dry reformingand steam reforming, respectively, the equilibrium amounts of H₂ and COin a synthesis gas can be different from the reaction stoichiometry. Theequilibrium amounts can be determined based on the water gas shiftequilibrium, which relates the concentrations of H₂, CO, CO₂ and H₂Obased on the reaction

H₂O+CO⇔H₂+CO₂  (4)

Most reforming catalysts, such as rhodium and/or nickel, can also serveas water gas shift catalysts. Thus, if reaction environment forproducing H₂ and CO also includes H₂O and/or CO₂, the initialstoichiometry from the reforming reaction may be altered based on thewater gas shift equilibrium. This equilibrium is also temperaturedependent, with higher temperatures favoring production of CO and H₂O.It is noted that higher temperatures can also improve the rate forreaching equilibrium. As a result, the ability to perform a reformingreaction at elevated temperatures can potentially provide severalbenefits. For example, instead of performing steam reforming in anenvironment with excess H₂O, CO₂ can be added to the reactionenvironment. This can allow for both a reduction in the ratio of H₂ toCO produced based on the dry reforming stoichiometry as well as areduction in the ratio of H₂ to CO produced based on the water gas shiftequilibrium. Alternatively, if a higher H₂ to CO ratio is desired, CO₂can be removed from the environment, and the ratio of H₂O to CH₄ (orother hydrocarbons) can be controlled to produce a desirable type ofsynthesis gas. This can potentially allow for generation of a synthesisgas having a H₂ to CO ratio of 0.1 to 15, or 0.1 to 3.0, or 0.5 to 5.0,or 1.0 to 10, by selecting appropriate amounts of feed components.

The reforming reactions shown in equations (1)-(3) are endothermicreactions. One of the challenges in commercial scale reforming can beproviding the heat for performing the reforming reaction in an efficientmanner while reducing or minimizing introduction of additionalcomponents into the desired synthesis gas product. Cyclic reactionsystems, such as reverse flow reactor systems, can provide heat in adesirable manner by having a cycle including a reforming step and aregeneration step. During the regeneration step, combustion can beperformed within a selected area of the reactor. A gas flow duringregeneration can assist with transferring this heat from the combustionzone toward additional portions of the reforming zone in the reactor.The reforming step within the cycle can be a separate step, so thatincorporation of products from combustion into the reactants and/orproducts from reforming can be reduced or minimized. The reforming stepcan consume heat, which can reduce the temperature of the reformingzone. As the products from reforming pass through the reactor, thereforming products can pass through a second zone that lacks a reformingor water gas shift catalyst. This can allow the reaction products tocool prior to exiting the reactor. The heat transferred from thereforming products to the reactor can then be used to increase thetemperature of the reactants for the next combustion or regenerationstep.

One common source for methane is natural gas. In some applications,natural gas, including associated hydrocarbon and impurity gases, may beused as a feed for the reforming reaction. The supplied natural gas alsomay be sweetened and/or dehydrated natural gas. Natural gas commonlyincludes various concentrations of associated gases, such as ethane andother alkanes, preferably in lesser concentrations than methane. Thesupplied natural gas may include impurities, such as H₂S and nitrogen.More generally, the hydrocarbon feed for reforming can include anyconvenient combination of methane and/or other hydrocarbons. Optionally,the reforming feed may also include some hydrocarbonaceous compounds,such as alcohols or mercaptans, which are similar to hydrocarbons butinclude one or more heteroatoms different from carbon and hydrogen. Insome aspects, an additional component present in the feed can correspondto impurities such as sulfur that can adsorb to the catalytic monolithduring a reducing cycle (such as a reforming cycle). Such impurities canbe oxidized in a subsequent cycle to form sulfur oxide, which can thenbe reduced to release additional sulfur-containing components (or otherimpurity-containing components) into the reaction environment.

In some aspects, the feed for reforming can include, relative to a totalweight of hydrocarbons in the feed for reforming, 5 wt % or more of C₂₊compounds, such as ethane or propane, or 10 wt % or more, or 15 wt % ormore, or 20 wt % or more, such as up to 50 wt % or possibly stillhigher. It is noted that nitrogen and/or other gases that arenon-reactive in a combustion environment, such as H₂O and CO₂, may alsobe present in the feed for reforming. In aspects where the reformercorresponds to an on-board reforming environment, such non-reactiveproducts can optionally be introduced into the feed, for example, basedon recycle of an exhaust gas into the reformer. Additionally oralternately, the feed for reforming can include 40 wt % or more methane,or 60 wt % or more, or 80 wt % or more, or 95 wt % or more, such ashaving a feed that is substantially composed of methane (98 wt % ormore). In aspects where the reforming corresponds to steam reforming, amolar ratio of steam molecules to carbon atoms in the feed can be 0.3 to4.0. It is noted that methane has 1 carbon atom per molecule whileethane has 2 carbon atoms per molecule. In aspects where the reformingcorresponds to dry reforming, a molar ratio of CO₂ molecules to carbonatoms in the feed can be 0.05 to 3.0.

Within the reforming zone of a reverse flow reactor, the temperature canvary across the zone due to the nature of how heat is added to thereactor and/or due to the kinetics of the reforming reaction. Thehighest temperature portion of the zone can typically be found near amiddle portion of the reactor. This middle portion can be referred to asa mixing zone where combustion is initiated during regeneration. Atleast a portion of the mixing zone can correspond to part of thereforming zone if a monolith with reforming catalyst extends into themixing zone. As a result, the location where combustion is startedduring regeneration can typically be near to the end of the reformingzone within the reactor. It is noted that the location of combustioncatalyst within the reactor(s) can overlap with the location ofreforming catalyst within the reactor(s), so that some portions of thereactor(s) can correspond to both combustion zone and reaction zone.Moving from the center of the reactor to the ends of the reactor, thetemperature can decrease. As a result, the temperature at the beginningof the reforming zone (at the end of the reactor) can be cooler than thetemperature at the end of the reforming zone (in the middle portion ofthe reactor).

As the reforming reaction occurs, the temperature within the reformingzone can be reduced. The rate of reduction in temperature can be relatedto the kinetic factors of the amount of available hydrocarbons forreforming and/or the temperature at a given location within thereforming zone. As the reforming feed moves through the reforming zone,the reactants in the feed can be consumed, which can reduce the amountof reforming that occurs at downstream locations. However, the increasein the temperature of the reforming zone as the reactants move acrossthe reforming zone can lead to an increased reaction rate.

At roughly 500° C., the reaction rate for reforming can be sufficientlyreduced that little or no additional reforming will occur. As a result,in some aspects as the reforming reaction progresses, the beginningportion of the reforming zone can cool sufficiently to effectively stopthe reforming reaction within a portion of the reforming zone. This canmove the location within the reactor where reforming begins to alocation that is further downstream relative to the beginning of thereforming zone. When a sufficient portion of the reforming zone has atemperature below 500° C., or below 600° C., the reforming step withinthe reaction cycle can be stopped to allow for regeneration.Alternatively, based on the amount of heat introduced into the reactorduring regeneration, the reforming portion of the reaction cycle can bestopped based on an amount of reaction time, so that the amount of heatconsumed during reforming (plus heat lost to the environment) is roughlyin balance with the amount of heat added during regeneration. After thereforming process is stopped, any remaining synthesis gas product stillin the reactor can optionally be recovered prior to starting theregeneration step of the reaction cycle.

The regeneration process can then be initiated. During regeneration, afuel such as methane, natural gas, or H₂, and oxygen can be introducedinto the reactor and combusted. The location where the fuel and oxidantare allowed to mix can be controlled in any convenient manner, such asby introducing the fuel and oxidant via separate channels. By delayingcombustion during regeneration until the reactants reach a centralportion of the reactor, the non-reforming end of the reactor can bemaintained at a cooler temperature. This can also result in atemperature peak in a middle portion of the reactor. The temperaturepeak can be located within a portion of the reactor that also includesthe reforming catalyst. During a regeneration cycle, the temperaturewithin the reforming reactor can be increased sufficiently to allow forthe reforming during the reforming portion of the cycle. This can resultin a peak temperature within the reactor of 1100° C. or more, or 1200°C. or more, or 1300° C. or more, or potentially a still highertemperature. The pressure in the reactor during regeneration can be aconvenient pressure, such as a pressure ranging from ambient (˜0 kPa-g)up to roughly 15 MPa-g.

The relative length of time and reactant flow rates for the reformingand regeneration portions of the process cycle can be selected tobalance the heat provided during regeneration with the heat consumedduring reforming. For example, one option can be to select a reformingstep that has a similar length to the regeneration step. Based on theflow rate of hydrocarbons, H₂O, and/or CO₂ during the reforming step, anendothermic heat demand for the reforming reaction can be determined.This heat demand can then be used to calculate a flow rate forcombustion reactants during the regeneration step. Of course, in otheraspects the balance of heat between reforming and regeneration can bedetermined in other manners, such as by determining desired flow ratesfor the reactants and then selecting cycle lengths so that the heatprovided by regeneration balances with the heat consumed duringreforming.

In addition to providing heat, the reactor regeneration step during areaction cycle can also allow for coke removal from the catalyst withinthe reforming zone. In various aspects, one or more types of catalystregeneration can potentially occur during the regeneration step. Onetype of catalyst regeneration can correspond to removal of coke from thecatalyst. During reforming, a portion of the hydrocarbons introducedinto the reforming zone can form coke instead of forming CO or CO₂. Thiscoke can potentially block access to the catalytic sites (such as metalsites) of the catalyst. In some aspects, the rate of formation can beincreased in portions of the reforming zone that are exposed to highertemperatures, such as portions of the reforming zone that are exposed totemperatures of 800° C. or more, or 900° C. or more, or 1000° C. ormore. During a regeneration step, oxygen can be present as thetemperature of the reforming zone is increased. At the temperaturesachieved during regeneration, at least a portion of the coke generatedduring reforming can be removed as CO or CO₂.

Due to the variation in temperature across the reactor, several optionscan be used for characterizing the temperature within the reactor and/orwithin the reforming zone of the reactor. One option for characterizingthe temperature can be based on an average bed or average monolithtemperature within the reforming zone. In practical settings,determining a temperature within a reactor requires the presence of ameasurement device, such as a thermocouple. Rather than attempting tomeasure temperatures within the reforming zone, an average (bed ormonolith) temperature within the reforming zone can be defined based onan average of the temperature at the beginning of the reforming zone anda temperature at the end of the reforming zone. Another option can be tocharacterize the peak temperature within the reforming zone after aregeneration step in the reaction cycle. Generally, the peak temperaturecan occur at or near the end of the reforming zone, and may be dependenton the location where combustion is initiated in the reactor.

Still another option can be to characterize the difference intemperature at a given location within the reaction zone at differenttimes within a reaction cycle. For example, a temperature difference canbe determined between the temperature at the end of the regenerationstep and the temperature at the end of the reforming step. Such atemperature difference can be characterized at the location of peaktemperature within the reactor, at the entrance to the reforming zone,at the exit from the reforming zone, or at any other convenientlocation.

In various aspects, the reaction conditions for reforming hydrocarbonscan include one or more of an average reforming zone temperature rangingfrom 400° C. to 1200° (or more); a peak temperature within the reformingzone of 800° C. to 1500° C.; a temperature difference at the location ofpeak temperature between the end of a regeneration step and the end ofthe subsequent reforming step of 25° C. or more, or 50° C. or more, or100° C. or more, or 200° C. or more, such as up to 800° C. or possiblystill higher; a temperature difference at the entrance to the reformingzone between the end of a regeneration step and the end of thesubsequent reforming step of 25° C. or more, or 50° C. or more, or 100°C. or more, or 200° C. or more, such as up to 800° C. or possibly stillhigher; and/or a temperature difference at the exit from the reformingzone between the end of a regeneration step and the end of thesubsequent reforming step of 25° C. or more, or 50° C. or more, or 100°C. or more, or 200° C. or more, such as up to 800° C. or possibly stillhigher.

With regard to the average reforming zone temperature, in variousaspects the average temperature for the reforming zone can be 500° C. to1500° C., or 400° C. to 1200° C., or 800° C. to 1200° C., or 400° C. to900° C., or 600° C. to 1100° C., or 500° C. to 1000° C. Additionally oralternately, with regard to the peak temperature for the reforming zone(likely corresponding to a location in the reforming zone close to thelocation for combustion of regeneration reactants), the peak temperaturecan be 800° C. to 1500° C., or 1000° C. to 1400° C., or 1200° C. to1500° C., or 1200° C. to 1400° C.

Additionally or alternately, the reaction conditions for reforminghydrocarbons can include a pressure of 0 psig to 1500 psig (10.3 MPa),or 0 psig to 1000 psig (6.9 MPa), or 0 psig to 550 psig (3.8 MPa); and agas hourly space velocity of reforming reactants of 1000 hr⁻¹ to 50,000hr⁻¹. The space velocity corresponds to the volume of reactants relativeto the volume of monolith per unit time. The volume of the monolith isdefined as the volume of the monolith as if it was a solid cylinder.

In some aspects, an advantage of operating the reforming reaction atelevated temperature can be the ability to convert substantially all ofthe methane and/or other hydrocarbons in a reforming feed. For example,for a reforming process where water is present in the reforming reactionenvironment (i.e., steam reforming or bi-reforming), the reactionconditions can be suitable for conversion of 10 wt % to 100 wt % of themethane in the reforming feed, or 20 wt % to 80 wt %, or 50 wt % to 100wt %, or 80 wt % to 100 wt %, or 10 wt % to 98 wt %, or 50 wt % to 98 wt%. Additionally or alternately, the reaction conditions can be suitablefor conversion of 10 wt % to 100 wt % of the hydrocarbons in thereforming feed, or 20 wt % to 80 wt %, or 50 wt % to 100 wt %, or 80 wt% to 100 wt %, or 10 wt % to 98 wt %, or 50 wt % to 98 wt %

In other aspects, for a reforming process where carbon dioxide ispresent in the reforming reaction environment (i.e., dry reforming orbi-reforming), the reaction conditions can be suitable for conversion of10 wt % to 100 wt % of the methane in the reforming feed, or 20 wt % to80 wt %, or 50 wt % to 100 wt %, or 80 wt % to 100 wt %, or 10 wt % to98 wt %, or 50 wt % to 98 wt %. Additionally or alternately, thereaction conditions can be suitable for conversion of 10 wt % to 100 wt% of the hydrocarbons in the reforming feed, or 20 wt % to 80 wt %, or50 wt % to 100 wt %, or 80 wt % to 100 wt %, or 10 wt % to 98 wt %, or50 wt % to 98 wt %.

In some alternative aspects, the reforming reaction can be performedunder dry reforming conditions, where the reforming is performed withCO₂ as a reagent but with a reduced or minimized amount of H₂O in thereaction environment. In such alternative aspects, a goal of thereforming reaction can be to produce a synthesis gas with a H₂ to COratio of 1.0 or less. In some aspects, the temperature during reformingcan correspond to the temperature ranges described for steam reforming.Optionally, in some aspects a dry reforming reaction can be performed ata lower temperature of between 500° C. to 700° C., or 500° C. to 600° C.In such aspects, the ratio of H₂ to CO can be 0.3 to 1.0, or 0.3 to 0.7,or 0.5 to 1.0. Performing the dry reforming reaction under theseconditions can also lead to substantial coke production, which canrequire removal during regeneration in order to maintain catalyticactivity.

EXAMPLES Impact of Modifying Flue Gas Exit Temperatures

A pilot scale reactor was used to investigate the impact and benefits ofmodifying flue gas exit temperatures on operation of a reverse flowreactor system. The examples provided herein correspond to results froma single reactor, but those of skill in the art will readily understandthe application of the following results to reaction systems includingplurality of reverse flow reactors.

One potential issue with selectively recycling high temperature flue gasis whether the increase in the input temperature of the recycle gascould alter the temperature profile within the reactor. To investigatethis, steam reforming was performed in the pilot scale reactor usingrepresentative steam reforming conditions, with three differenttemperatures for the input gas flow. The input gas temperaturescorresponded to 180° C., 240° C., and 280° C.

FIGS. 7-9 show the results from the investigation. FIG. 7 shows theamount of methane conversion during steam reforming as a function ofcycle length for each of the three inlet gas temperatures. As shown inFIG. 7, the conversion percentage for the methane was substantially thesame at each inlet gas temperature. It is believed that the results inFIG. 7 would be similar at substantially higher inlet gas temperatures,such as inlet gas temperatures of 400° C. or more, or 500° C. or more,such as up to 700° C. or possibly still higher.

FIG. 8 shows how the gas composition during regeneration changes withinlet feed temperature. In FIG. 8, the left axis corresponds to theamount of H₂ (orange dots) that was needed to achieve the targettemperature profile in the reactor. The right axis (blue dots)corresponds to a ratio of the gas flow during the regeneration stepversus the methane flow during the reforming step. As shown in FIG. 8,the amount of hydrogen required to achieve the desired temperatureprofile was reduced as the inlet gas temperature was increased. Thereduced amount of hydrogen fuel during regeneration contributed to thelower total flow required during the regeneration step to convert themethane flow during the reforming step.

Based on FIGS. 7 and 8, increasing the inlet gas temperature duringregeneration allowed the conversion rate of methane during steamreforming to be maintained while using less fuel and less gas flowduring the regeneration step. FIG. 9 shows the temperature profiles thatwere produced within the reactor for each inlet gas temperature. Asshown in FIG. 9, the temperature profile was substantially similar foreach inlet gas temperature. Thus, FIGS. 7-9 demonstrate that increasingthe inlet gas temperature during regeneration can allow substantiallythe same temperature profile and reaction conditions to be achieved at alower fuel cost. This increase in inlet gas temperature can be achievedby segregating available flue gas so that high temperature flue gas ispreferentially recycled for use as the inlet gas during regeneration.

FIGS. 7-9 demonstrate that substantially the same desired reactionconditions can be achieved during the reaction step at varioustemperature values for the inlet gas during the regeneration step. FIGS.10 and 11 further demonstrate the benefits that can be achieved byvarying the inlet gas temperature.

FIG. 10 shows the temperature profile from performing steam reforming inthe reactor with a flue gas exhaust temperature of roughly 450° C.,while FIG. 11 shows results from performing steam reforming with a fluegas exhaust of roughly 600° C. The temperature profiles are shown atboth the end of the regeneration step and the end of the reaction(reforming) step. The temperature profiles are plotted relative todistance from the top of the reactor.

As shown in FIG. 10 and FIG. 11, the temperature profiles in FIGS. 10and 11 are similar in the region between 0 inches-4 inches in thereactor. This corresponds to the portion of the reactor that is closestto where the regeneration gas flow is introduced into the reactor.However, the catalyst section where reforming occurs within the reactorcorresponds to the region between roughly 4 inches and 12 inches. Inthis portion of the reactor, having a higher flue gas exit temperatureresults in a higher temperature at the end of the regeneration step andat the end of the reforming step at each location sampled within thereactor.

The differences in the temperature profiles in FIG. 10 and FIG. 11illustrates the benefits of operating at a higher flue gas exittemperature. In the region between 0 inches and 4 inches, thetemperature profile is constrained based on the limits of the structuralmaterials used for the reactor. Because temperatures substantially above1200° C. are not desirable, the amount of fuel that can be combusted perunit time during regeneration is constrained. Thus, similar temperatureprofiles near the top of the reactor were obtained at either flue gasexit temperature. However, further down the reactor where the catalystis located, the constraint of limiting the flue gas exhaust temperatureto a temperature of roughly 450° C. resulted in a limit on thetemperature profile in the region between 4 inches and 12 inches in thereactor. When the constraint on the flue gas exhaust temperature wasrelaxed to allow an exit temperature of roughly 600° C., a correspondingincrease in temperature was observed across the catalyst region.

FIG. 10 and FIG. 11 show the difference in temperature profile withinthe reactor when operating the reactor to have a flue gas exittemperature of 450° C. versus 600° C. Table 1 shows the regenerationinput flows that were used to produce the temperature profiles shown inFIG. 10 and FIG. 11.

TABLE 1 Reforming Results Versus Regeneration Exhaust Temperature Valuescorrespond to standard cubic FIG. 10 T FIG. 11 T feet per minuteprofiles profiles Air 3.2 5.7 N₂ 7.2 10.9 H₂ 1.1 1.9 Total Flow 11.518.5 XH2 0.1 0.1 Average Conversion 52% 76%

As shown in Table 1, in order to achieve the regeneration temperatureprofile in FIG. 11, an increased amount of gas flow was used during theregeneration step relative to the input gas flow for FIG. 10. It isnoted that a small excess of H₂ was included in the gas flow (XH2)relative to the stoichiometric combustion amount. The increased flow toachieve the temperature profile in FIG. 11 included increasing theamount of H₂, therefore allowing more heat to be added to the reactorduring regeneration. This additional heat allowed for a substantialincrease in the amount of methane converted during the reforming portionof the reaction cycle, from 52% conversion to 76% conversion. It isnoted that for the purpose of this example, the temperature profileswere selected to have less than 90% conversion, so that the benefits ofincreasing the flue gas exhaust temperature would be clear. In otheraspects, increases in the flue gas exhaust temperature can be used withreforming conditions that result in 90% or more conversion of methaneand/or other hydrdocarbons. In such a situation where the conversion isalready relatively high, increasing the amount of heat available in thereactor can allow for reforming of an increased amount of methane and/orother hydrocarbons.

ADDITIONAL EMBODIMENTS Embodiment 1

A method for operating a plurality of reactors, comprising: reacting afirst mixture comprising fuel and 0.1 vol % or more of O₂ under firstcombustion conditions in a first combustion zone within a first reactorto form a first flue gas comprising a first temperature of 350° C. ormore, and to heat one or more surfaces in a first reaction zone to aregenerated surface temperature of 800° C. or more, the first reactionzone comprising a catalyst composition; passing at least a portion ofthe first flue gas and at least a portion of a second flue gas into asecond reactor;

reacting a second mixture comprising fuel, 0.1 vol % or more of O₂, theat least a portion of the first flue gas, and the at least a portion ofthe second flue gas under second combustion conditions in a secondcombustion zone within the second reactor to form the second flue gas,the second flue gas having a temperature of between 200° C. to the firsttemperature, and to heat one or more surfaces in a second reaction zone,the second mixture comprising a volume ratio of the at least a portionof the first flue gas to the at least a portion of the second flue gasof 1.5 or more; exposing a first reactant stream to the one or moresurfaces in the first reaction zone to increase the temperature of thefirst reactant stream; and exposing the first reactant stream to thecatalyst composition in the first reaction zone at a temperature of 800°C. or more to form a first product stream, a direction of flow for thefirst reactant stream within the first reaction zone being reversedrelative to a direction of flow for the first mixture.

Embodiment 2

The method of Embodiment 1, wherein the method further comprises:exhausting the first flue gas from the first reactor into a manifold ata first exhaust location, the manifold comprising an expander outlet anda recycle outlet; exhausting the second flue gas from the second reactorinto the manifold at a second exhaust location, the second exhaustlocation being closer to the expander outlet than the first exhaustlocation along a manifold flow path during the exhausting of the firstflue gas and the exhausting of the second flue gas; and withdrawing theat least a portion of the first flue gas and the at least a portion ofthe second flue gas from the recycle outlet prior to the passing the atleast a portion of the first flue gas and the at least a portion of thesecond flue gas into the second reactor.

Embodiment 3

The method of Embodiment 2, wherein the method further comprisescompressing the at least a portion of the first flue gas and the atleast a portion of the second flue gas after the withdrawing; or whereinthe method further comprises at least one of closing a valve and openinga valve to modify the manifold flow path; or a combination thereof

Embodiment 4

The method of any of the above embodiments, wherein passing at least aportion of the first flue gas into the second reactor comprises: passinga first portion of the first flue gas into the first reactor; andpassing a second portion of the first flue gas into the second reactor.

Embodiment 5

The method of any of the above embodiments, wherein after the reactingthe second mixture in the second reactor, the method further comprises:reacting a third mixture comprising fuel and 0.1 vol % or more of O₂under first combustion conditions in the second combustion zone withinthe second reactor to form a third flue gas comprising the firsttemperature, and to heat the second reaction zone to the regeneratedsurface temperature, the second reaction zone comprising a catalystcomposition; passing at least a portion of the third flue gas and atleast a portion of an additional flue gas into an additional reactor;reacting a fourth mixture comprising fuel, 0.1 vol % or more of O₂, theat least a portion of the third flue gas, and the at least a portion ofthe additional flue gas under second combustion conditions in anadditional combustion zone within the additional reactor to form theadditional flue gas, the additional flue gas having a temperaturebetween 200° C. to the first temperature, and to heat one or moresurfaces in an additional reaction zone, the fourth mixture comprising avolume ratio of the at least a portion of the third flue gas to the atleast a portion of the additional flue gas of 1.5 or more; and after thereacting of the third mixture, exposing a second reactant stream to thecatalyst composition in the second reaction zone at the regeneratedsurface temperature to form a second product stream, a direction of flowfor the second reactant stream within the second reaction zone beingreversed relative to a direction of flow for the third mixture, thethird mixture optionally comprising substantially the same compositionas the first mixture.

Embodiment 6

The method of any of the above embodiments, wherein the catalystcomposition comprises a reforming catalyst.

Embodiment 7

The method of Embodiment 6, wherein the first reactant stream comprisesa reformable hydrocarbon and steam, and wherein the first product streamcomprises hydrogen, the reformable hydrocarbon optionally comprisingmethane.

Embodiment 8

The method of any of the above embodiments, wherein the second mixturecomprises a volume ratio of the at least a portion of the first flue gasto the at least a portion of the second flue gas of 3.0 or more.

Embodiment 9

The method of any of the above embodiments, wherein the first reactorand the second reactor comprise reverse flow reactors; or wherein thefirst reactor and the second reactor comprise reactor systems, eachreactor system comprising a recuperator portion including the combustionzone and a second portion including the reaction zone; or a combinationthereof

Embodiment 10

A system comprising a plurality of reverse flow reactors, comprising: amanifold comprising a loop flow path, a recycle outlet, a second outlet,a first loop valve, and a second loop valve, the second outlet beinglocated between the first loop valve and the second loop valve; aplurality of reverse flow reactors, each reverse flow reactor comprisinga recycle gas inlet, a recycle gas inlet valve, a flue gas outlet, and aflue gas outlet valve, the flue gas outlet valve of each reverse flowreactor being in fluid communication with the manifold, the flue gasoutlet of at least one reverse flow reactor being in fluid communicationwith the manifold via an open flue gas outlet valve; and a recyclecompressor in fluid communication with the recycle outlet and eachrecycle gas inlet valve, the recycle gas inlet of the at least onereverse flow reactor being in fluid communication with the recyclecompressor via an open recycle gas inlet valve.

Embodiment 11

The system of Embodiment 10, further comprising an expander in fluidcommunication with the second outlet.

Embodiment 12

The system of Embodiment 10 or 11, wherein the plurality of reverse flowreactors comprise a combustion zone and a reaction zone, the reactionzone optionally comprising a reforming catalyst.

Embodiment 13

The system of any of Embodiments 10 to 12, wherein the first loop valveis closed and the second loop valve is open, or wherein the second loopvalve is closed and the first loop valve is open.

Embodiment 14

The system of any of Embodiments 10 to 13, wherein a plurality ofreverse flow reactors are in fluid communication with the recyclecompressor via a plurality of open recycle gas inlet valves.

While the present invention has been described and illustrated byreference to particular embodiments, those of ordinary skill in the artwill appreciate that the invention lends itself to variations notnecessarily illustrated herein. For this reason, then, reference shouldbe made solely to the appended claims for purposes of determining thetrue scope of the present invention.

1. A method for operating a plurality of reactors, comprising: reactinga first mixture comprising fuel and 0.1 vol % or more of O₂ under firstcombustion conditions in a first combustion zone within a first reactorto form a first flue gas comprising a first temperature of 350° C. ormore, and to heat one or more surfaces in a first reaction zone to aregenerated surface temperature of 800° C. or more, the first reactionzone comprising a catalyst composition; passing at least a portion ofthe first flue gas and at least a portion of a second flue gas into asecond reactor; reacting a second mixture comprising fuel, 0.1 vol % ormore of O₂, the at least a portion of the first flue gas, and the atleast a portion of the second flue gas under second combustionconditions in a second combustion zone within the second reactor to formthe second flue gas, the second flue gas having a temperature of between200° C. to the first temperature, and to heat one or more surfaces in asecond reaction zone, the second mixture comprising a volume ratio ofthe at least a portion of the first flue gas to the at least a portionof the second flue gas of 1.5 or more; exposing a first reactant streamto the one or more surfaces in the first reaction zone to increase thetemperature of the first reactant stream; and exposing the firstreactant stream to the catalyst composition in the first reaction zoneat a temperature of 800° C. or more to form a first product stream, adirection of flow for the first reactant stream within the firstreaction zone being reversed relative to a direction of flow for thefirst mixture.
 2. The method of claim 1, wherein the method furthercomprises: exhausting the first flue gas from the first reactor into amanifold at a first exhaust location, the manifold comprising anexpander outlet and a recycle outlet; exhausting the second flue gasfrom the second reactor into the manifold at a second exhaust location,the second exhaust location being closer to the expander outlet than thefirst exhaust location along a manifold flow path during the exhaustingof the first flue gas and the exhausting of the second flue gas; andwithdrawing the at least a portion of the first flue gas and the atleast a portion of the second flue gas from the recycle outlet prior tothe passing the at least a portion of the first flue gas and the atleast a portion of the second flue gas into the second reactor.
 3. Themethod of claim 2, further comprising compressing the at least a portionof the first flue gas and the at least a portion of the second flue gasafter the withdrawing.
 4. The method of claim 2, further comprising atleast one of closing a valve and opening a valve to modify the manifoldflow path.
 5. The method of claim 1, wherein passing at least a portionof the first flue gas into the second reactor comprises: passing a firstportion of the first flue gas into the first reactor; and passing asecond portion of the first flue gas into the second reactor.
 6. Themethod of claim 1, wherein after the reacting the second mixture in thesecond reactor, the method further comprises: reacting a third mixturecomprising fuel and 0.1 vol % or more of O₂ under first combustionconditions in the second combustion zone within the second reactor toform a third flue gas comprising the first temperature, and to heat thesecond reaction zone to the regenerated surface temperature, the secondreaction zone comprising a catalyst composition; passing at least aportion of the third flue gas and at least a portion of an additionalflue gas into an additional reactor; reacting a fourth mixturecomprising fuel, 0.1 vol % or more of O₂, the at least a portion of thethird flue gas, and the at least a portion of the additional flue gasunder second combustion conditions in an additional combustion zonewithin the additional reactor to form the additional flue gas, theadditional flue gas having a temperature between 200° C. to the firsttemperature, and to heat one or more surfaces in an additional reactionzone, the fourth mixture comprising a volume ratio of the at least aportion of the third flue gas to the at least a portion of theadditional flue gas of 1.5 or more; and after the reacting of the thirdmixture, exposing a second reactant stream to the catalyst compositionin the second reaction zone at the regenerated surface temperature toform a second product stream, a direction of flow for the secondreactant stream within the second reaction zone being reversed relativeto a direction of flow for the third mixture.
 7. The method of claim 6,wherein the third mixture comprises substantially the same compositionas the first mixture.
 8. The method of claim 1, wherein the catalystcomposition comprises a reforming catalyst.
 9. The method of claim 8,wherein the first reactant stream comprises a reformable hydrocarbon andsteam, and wherein the first product stream comprises hydrogen.
 10. Themethod of claim 9, wherein the reformable hydrocarbon comprises methane.11. The method of claim 1, wherein the second mixture comprises a volumeratio of the at least a portion of the first flue gas to the at least aportion of the second flue gas of 3.0 or more.
 12. The method of claim1, wherein the first reactor and the second reactor comprise reverseflow reactors.
 13. The method of claim 1, wherein the first reactor andthe second reactor comprise reactor systems, each reactor systemcomprising a recuperator portion including the combustion zone and asecond portion including the reaction zone.
 14. A system comprising aplurality of reverse flow reactors, comprising: a manifold comprising aloop flow path, a recycle outlet, a second outlet, a first loop valve,and a second loop valve, the second outlet being located between thefirst loop valve and the second loop valve; a plurality of reverse flowreactors, each reverse flow reactor comprising a recycle gas inlet, arecycle gas inlet valve, a flue gas outlet, and a flue gas outlet valve,the flue gas outlet valve of each reverse flow reactor being in fluidcommunication with the manifold, the flue gas outlet of at least onereverse flow reactor being in fluid communication with the manifold viaan open flue gas outlet valve; and a recycle compressor in fluidcommunication with the recycle outlet and each recycle gas inlet valve,the recycle gas inlet of the at least one reverse flow reactor being influid communication with the recycle compressor via an open recycle gasinlet valve.
 15. The system of claim 14, further comprising an expanderin fluid communication with the second outlet.
 16. The system of claim14, wherein the plurality of reverse flow reactors comprise a combustionzone and a reaction zone.
 17. The system of claim 16, wherein thereaction zone comprises a reforming catalyst.
 18. The system of claim14, wherein the first loop valve is closed and the second loop valve isopen, or wherein the second loop valve is closed and the first loopvalve is open.
 19. The system of claim 14, wherein a plurality ofreverse flow reactors are in fluid communication with the recyclecompressor via a plurality of open recycle gas inlet valves.